Facile methods to manufacture intelligent graphene nanomaterials and the use of for super-light machine and vehicles

ABSTRACT

This utility invention is to replace some of the parts of current vehicles and robotic machines with intelligent graphene-based fibers and nanocomposites to achieve significantly weight-decreasing and energy-savings. This invention also is related to the formation of new generation vehicles, machine parts including robotics, which include but not limited to all kinds of cars, trailers, trucks, vehicles on roads and in the sky, ships on the ocean, and intelligent robotics for Human, as well as computer parts, bicycles, and sports supplies.

FIELD OF THE INVENTION

The present invention is mostly related to substitution parts oftraditional vehicle parts both running on the roads, in the sky, and onthe ocean with graphene-based carbon fibers, intelligent graphenecomposites, and the use thereof for the method to prepare the parts,which includes molding and smart additive manufacturing 3D printing forthe parts and articles to those vehicles and machines.

BACKGROUND

Running most current vehicles on the roads, especially heavy-dutytrailers, trains, and trucks, normally involves burning huge amounts offossil fuels, which leads massive pollution released to the air. Thiscauses air pollution problems, such as PM 2.5, PM 10, and much more inmany countries. According to the published report on Aug. 26, 2015 fromEnvironmental and Energy Study Institute (EESI). “transporting peopleand goods accounts for 1.8 trillion tons, or 27 percent, of U.S.greenhouse gas (GHG) emissions and approximately 70 percent of all U.S.oil use (or about 13.1 million barrels of oil per day, excludingbiofuels). With the burning of gasoline and diesel accounting for 59percent and 24 percent of the transportation sector's emissions,respectively, significant reductions in auto and truck emissions areessential to climate change mitigation efforts.” Currently, vehicle fuelefficiency can be as low as only about 40%. An advanced design couldincrease the efficiency to 80%. Aerodynamics and weight reductionthrough lighter materials using carbon fiber and lighter metals enablesmanufacturers to reduce vehicle weight and increase engine efficiency,while maintaining durability and strength. Meanwhile, thinner andsmaller wheels and low rolling resistance tires reduce road friction andair drag, increasing fuel mileage.

On the other hand, there are tremendous demands in decreasing weightwhile maintaining the mechanical strength in the field of automobiles,airplanes, boat, ships in the ocean, and the underdeveloped intelligentrobotic human machines, as well as computer and sport parts etc.Manufacturers have begun to use carbon fibers to replace heavy steelplates/boards for trailers and trucks, cars, and the machines mentionedabove. Carbon fiber reinforced parts are light, strong and load-bearing,structural parts. Cutting weight from cars is important, as automakerspush to hit Corporate Average Fuel Economy standards of more than 54.5mpg by 2025. Using carbon fibers to replace some parts of traditionaltrailers have been proved to be able decrease the weight up to 40% ofthe vehicles. However, currently commercialized carbon fibers normallyare made from carbon-rich polymers such as polyacrylonitrile (“PAN”)(U.S. Pat. No. 8,808,597, 2014), which are currently very expensive toproduce, because it is synthesized from petroleum products through theoil-refining manufacturing process, which has resulted in carbon fibervehicles being only at early stage marketing concepts. There is animperative need to find substitutions for PAN or PAN-produced carbonfibers to overcome the significant pollution, high energy-demand, andtime-consumption problems that are factors in the conventional carbonfiber production methods.

Our present invention provides an innovative technology in usinggraphene-based carbon fibers and graphene composites to combine with, orto substitute, the traditional PAN-produced carbon fibers, which candramatically decrease the manufacture cost.

SUMMARY OF THE INVENTION

The present invention uses graphene-based carbon fibers andgraphene-based three dimensional nanostructure composites to flexiblyform the parts for vehicles and machines, which are mostly obtained fromnatural graphite. To achieve certain functions and properties,utilization of nanomaterials such as nanopowder of metal oxides or metalnanowires, and nano-cellulose along with graphene are used to formcomposite fibers or composite mixtures. Once the fibers are produced,they may be used to form the desired machine parts by either moldingwith proper resin or by integration with 3D additive manufacturingprinting directly. Graphene carbon fibers may be treated by properannealing in special gases and inert or reduction environment, resultingin high quality intelligent fiber composites, with significantly lowercost throughout the entire process. This facile method innovates thebroad formation of large amount of light weight metal composites, andfunctional nanofibers with proper metal oxide nanophases joined forunique applications. This decreases the carbon fiber costs whileenhancing the final products' properties favorably. This invention alsoproduces a large amount of new graphene composites for the creation andenhancement of anti-corrosion platforms, as well as for the enhancedhigh mechanical properties' body parts for electrical vehicles andmachines. This invention represents an opportunity to provide energysavings, greener chemical process manufacturing, and lower the cost forelectrical vehicles, parts of airplanes, as well as ships in the ocean.

The present invention works by using one step to form high qualitygraphene-based molding parts through the use of graphene carbon fibersand nanocomposite materials and their combinations.

The purpose of the invention is to provide a method to manufacturegraphene-based parts by using graphene intelligent carbon fibers, orporous three-dimensional graphene based nanocomposite sheets orgraphene-nanocomposites suspensions through molding and green chemical3D additive manufacturing printing process.

Another purpose of the invention is to provide large amounts of designedparts of graphene-based nanocarbon composites for new field applicationsfor intelligent robotic human, trucks, trailers, trains, buses, trams,vans, cars, airplanes, computer cases and mother boards, as well asboats and ships in the ocean, and anti-corrosion pipes for liquidstransportation including chemicals and oil-refining pipes.

A further purpose of the invention is to allow for the vehicle partsmanufacturing at low temperature, which does not have as much waste andpollution released to the environment as current methods.

Another purpose of the invention is to significantly decrease therequired manufacturing time to produce the designed parts.

A further purpose of the invention is to decrease the requirements ofequipment for the manufacture of machine parts and articles for vehiclesthrough additive manufacturing 3D printing.

Another purpose of the invention is to produce graphene-based parts orarticles that may be created with the addition of other elements orcompositions which can be used to create products which have a broadrange of unique and enhanced functional properties, such asthermo-conductivity, electric conductivity, resistance to corrosion, andmany other properties that will be able to be used to improveelectronics, energy efficiency, lower environmental impact, andincreased product lifespan.

A further purpose of the invention is to reduce the reliance on oil andpetroleum to create carbon fiber.

BRIEF DESCRIPTION OF THE DRAWINGS

The utility method shall be hereby described in detail in thedescription with reference to the attached drawings, in which:

FIG. 1 is a flowchart showing a method of manufacturing graphene-basedcarbon fibers and its sheets by a “cotton-candy machine” throughspinning, according to the present invention; and

FIG. 2 is a flowchart showing a method of manufacturing graphene carbonfiber-based vehicle parts and articles for robotics and ships throughmolding.

FIG. 3 is a flowchart showing a method of manufacturinggraphene-nanocomposite parts or articles by a commercialized additivemanufacturing 3D printing machine according to the present invention:

FIG. 4 is a flowchart showing a method of manufacturing porous graphenenanocomposite sheets or plates;

FIG. 5 is a flowchart showing a method of manufacturing graphene-basednanocomposite parts or articles using porous graphene sheets throughmolding;

FIG. 6 provides a view of graphene fibers for use in machine parts;

FIG. 7 provides a view of graphene gel and a cured graphene machinepart;

FIG. 8 provides an example of Graphene-based wagon and trolley model:decreasing conventional steel wagon 80% body weight, and printed bygraphene filament: C %=82% in atomic percentage; and

FIG. 9 shows graphene-plastic foams that can be cut into shapes to formintelligent machine parts or articles that lightens the weight ofvehicles.

DETAILED DESCRIPTION OF THE INVENTION

The aforementioned goals are achieved by the present invention usinggraphene-based carbon fibers, graphene-based porous nanocompositeplates, or graphene-based nanocomposite suspensions for solutionprinting through additive manufacturing 3D printing technologycontrolled by computer software, respectively. The following sectionsgive our three approaches to demonstrate our innovative technology forgraphene applications to machine and vehicles.

Approach I Using Graphene-Based Carbon Fibers as Starting Materials

Graphene flake powder or graphene oxide powder is used as graphenematerial to start this process. Disperse the graphene powder intosolvent with the assistant of surfactants, and add a small amount ofnanocellulose fibers, polymers, or resins plus additives into thesolution under stirring to obtain a uniform viscosity mixture forspinning.

Examples of solvents that may be used in the present invention as notedabove and elsewhere herein include, but are not limited to: water,alcohols, acetone, ketones, dimethyl formamide (DMF), ethylene glycol(EG). DMSO, and their co-solvents, but prefer water and alcohols for thegreen chemical manufacturing.

Examples of polymers that may be used as noted above and elsewhereherein include, but are not limited to: high carbon contented polymersare preferred to be additives, but not limited. Polymers can be such aspolyacrylonitrile (PAN), polystyrene, portion of asphalt, epoxy,polycarbonate, and any kinds of celluloses, polyvinyl alcohol (PVA),polyurethane, polyvinyl chloride (PVC), polyethylene (PE), andpolyethylene glycol, nylon, polydimethylsiloxane, polyacrylamide, andpoly(methyl methacrylate) (PMMA), and the like.

Examples of resins that may be used as noted above and elsewhere hereininclude, but are not limited to: polyvinyl resin, polyester resin,epoxy, polycarbonate resin, polyurethane resins, silicone resin,poly(methyl methacrylate) resin, and epoxy siloxane resins.

Graphene-based carbon fibers can be prepared using solution spinningthough a solution spinning machine like a cotton candy machine. Then,the cotton-candy-made graphene carbon fibers are first treated inreduction/functional gas flow environment for annealing at temperaturefrom 200 to 2000° C., preferring 1800° C. for about 4 hours byprogramming control. The flow gases could be, but are not limited tomethane, benzene, alkanes, and hydrogen, ammonia, and so on. Thisprocess is to enhance the carbon fibers' mechanical properties and thesurface treatment for functional groups to enhance the interfacechemical functional groups formation. In some cases, polymer withfunctional groups that can form passivation layers on thosegraphene-based carbon fibers will be employed for the surface treatment.

Graphene fiber sheets can be obtained by placing the treatedcotton-candy graphene fibers under vacuum. The graphene carbon fibersheets can be also prepared from our previous invention innon-provisional U.S. patent application Ser. No. 15/441,972 filed onFeb. 24, 2017. This application Ser. No. 15/441,972 filed on Feb. 24,2017 is incorporated herein by reference in its entirety and for any andall purposes as if fully set forth herein. Similarly. U.S. provisionalapplication No. 62/322,084 filed on Apr. 13, 2016 is incorporated hereinby reference in its entirety and for any and all purposes as if fullyset forth herein.

To prepare the graphene-based carbon fibers parts or articles forvehicles and machines, the treated graphene carbon fiber sheets are cutinto desired shape and placed in vacuum for molding as desired models.Based on the thickness needs, three to five or more sheets may bestacked together in the models. Then, under vacuum, a resin, such asthose discussed above will be injected to wet the entire graphene carbonfiber sheets. The resin may then be cured at about 20 to 400° C.,preferring 250° C., the graphene-based carbon fibers part or article isformed, and ready to be used for machines or vehicles. The article has asimilar mechanical strength as steel has.

Approach II Using Graphene Flakes or Graphene Oxide Flakes as StartingMaterials

Graphene flake powder or graphene oxide powder is used as graphenematerial to start this process. Disperse the graphene powder intosolvent, such as those discussed above, with the assistance ofsurfactants, and add a small amount of nanocellulose fibers, polymers,such as those discussed above, or resins, such as the ones noted above,plus additives into the solution under stirring to obtain the uniformviscosity mixture for solution printing. These materials may be similaror the same as the options noted above for Approach 1.

Next, inject the mixed solutions for additive manufacturing 3D printingand print it as inks through nozzles to form the designed parts orarticles for robotics, vehicles, tram (e.g. side walls or hoods), andship parts or electrical cars, airplane, or trains with railway or notrack-railway advanced trains (e.g. non-railway track magnetic trainsthat is under developed in USA). In a particular embodiment, thegraphene based carbon fiber material may be formed into a filament foruse in a 3D printer. As such, intelligent articles can be constructed by3D printing using graphene-based composite filament via 3D printers orusing non-solvent graphene-epoxy composites for 3D printing using lightcuring.

Third, after printing, slightly heat the printed wet parts to about 20to 400° C. (preferring 250° C.), the wet parts become hard due to thecuring of the resin from the mixture in the graphene nanocomposites. Theformation of 3D networks through chemical bonds after the curingsignificantly enhances the mechanical strength and other properties. Thestructures of this type of graphene-based nanocomposites are ofthree-dimensional chemically bonded networks inside the nanostructures,which makes the composites uniform in molecular level, and crosslinkedtightly, mechanical strength that is competed with steel, which areessential to the parts of heavy duty vehicles that ensures its durableand lifespan.

Further, to achieve unexpected new properties, the mixture may furthercontain small amount of additives such as nanoparticles or nanowires ofmetal or non-metals, or steel nano-powder, and metal oxide. Examples mayinclude but are not limited to carbon nanotubes, Mg, Al, steel alloypowder, ZrO₂, Fe₃O₄, or MoS₂, WS₂, their combination would be used tomix with graphene flakes, proper polymer, and cellulose to form themixed suspensions before 3D printing.

Examples of the small amount of additives to achieve unique propertiesof the graphene nanocomposite parts or articles for vehicles mayinclude, but are not limited to: nanoparticles or nanowires of metal orsteel nano-powder, and metal oxide, examples are not limited to carbonnanotubes, Mg, Al, steel alloy powder, ZrO₂, Fe₃O₄, or MoS₂, WS₂, MgO,Al₂O₃, or their combination. These additives may, among other uses, beused to mix with graphene flakes, proper polymer, and nanocellulose toform the mixed suspensions before 3D printing.

Approach III Using Graphene-Based Porous Nanocomposites as StartingMaterials

Based on the processing temperature and additives, different mechanicalproperties of graphene-based carbon nanoporous composite sheets can beformed through the use of suspensions by adding additional foam-agentsto the mixture of Approach II. The porous sheets can be prepared bydirectly pouring the pore-forming-agent-containing suspensions into amold, leaving it or heating it from room temperature 20 to 400° C. toform porous sheets, preferring 250° C. The porous sheets are thenannealed in inert or flow gases and special reduction gas flow in atemperature range of 400° C. to 2000° C., preferring 1800° C. Theprepared graphene porous sheet has high surface area, extremely hightensile and Young's modulus. Pore sizes are in the range of 1 nm to 8μm.

Examples of the foam/pore forming agent may include but are not limitedto any substances generally releasing a gas. These may be an organicpolymeric material or an organic small-molecule material having adecomposition temperature lower than 2000° C. or inorganic smallmolecules; these can include, but are not limited to: colophony, helium,ammonium carbonate, carbon dioxide, tetramethyl ammonium acetate,hydrogen, nitrogen, sodium bicarbonate, ammonium acetate, peroxide,ammonium nitrate, basic cupric carbonate, and the like.

To prepare the graphene-based carbon nanocomposite parts or articles forvehicles and machines, the treated graphene porous carbon sheets are cutinto desired shape and placed in vacuum for molding as desired. Based onthe thickness needs, three to five or more sheets may be stackedtogether in the mold. Then, under vacuum, resin, such as those notedabove, will be injected to wet the entire graphene carbon fiber sheets.After the resin is cured at room temperature to about 400° C.(preferring 250° C.), the graphene-based carbon fibers part or articleis formed, and ready to be used for machines or vehicles. The articleshave compete mechanical strength as steel has, light weight as carbonfibers, much lighter than alloy of Al—Mg, and have a variety of uniqueproperties. It has excellent mechanical properties such as strength, andadjustable properties for thermal and electrical conductivities,shielding radiations, and electromagnetic waves, anti-corrosion, andmore unique properties.

In summary, our invention leads to large a number of graphene-basednanocomposite parts or articles formed for machines, robotics,airplanes, ships, and vehicles (cars, trucks, trailers, vans etc.) plustram and trains, which have compete mechanical strength as steel, lightweight as carbon fibers, much lighter than alloy of Al—Mg, and have avariety of unique properties. It has excellent mechanical propertiessuch as strength, and adjustable properties for thermal and electricalconductivities, shielding radiations, and electromagnetic waves,anti-corrosion, and more.

Referring now to FIG. 1 showing the operational flowchart of the methodof manufacturing graphene into carbon fiber according to the presentinvention. As shown in FIG. 1 , the method of the present inventiongenerally comprises the steps of obtaining graphene flakes or grapheneoxide S10, forming the fibers via cotton-candy machine or similar setupfor spinning S20, and applying a heat treatment between 200° C. to 2000°C., preferring 1800° C. S30. By altering the heat treatment applied, thequalities of the resulting carbon fiber can be manipulated and enhanced;finally graphene-based carbon fiber sheet is prepared by placing theas-prepared graphene carbon fibers in vacuum molds S40.

FIG. 2 shows the operational flowchart of the method of manufacturinggraphene carbon fiber sheets to form vehicle parts or articles accordingto the present invention. As shown in FIG. 2 , the method of the presentinvention generally comprises the steps of obtaining graphene carbonfiber sheet in a mold S10, forming the fiber sheet stacks viaover-layering them S20, forming the parts or articles by applying vacuumin the mold, injecting resin to cure at 20 to 400° C. preferring 250° C.S30, and applying the parts or articles to the desired vehicles S40. Ina preferred embodiment and curing of the present invention the heatingprocess heats the fibers up to 400° C., preferring 250° C. in air S30.

FIG. 3 shows the operational flowchart of the method of manufacturinggraphene-based nanocomposite parts or articles through additivemanufacturing 3D printing according to the present invention. As shownin FIG. 3 , the method of the present invention generally comprises thesteps of obtaining graphene flakes or graphene oxide S10, forming theuniform suspension in solvent with small amount resin and otheradditives S20, applying adaptive 3D printing technology S30 via anAdaptive 3D Printer with digital control through a computer, applying afurther heat treatment between 20 to 400° C., preferring 250° C. forcuring S40, and applying a further heat treatment heated to 400 to 2000°C., preferring 1800° C. in inert/flow gas environment S50 which resultsin a further refined and crosslinking formation inside thenanocomposites.

FIG. 4 shows the operational flowchart of the method of manufacturingporous graphene nanocomposite sheets or plates according to the presentinvention. The method of the present invention generally comprises thesteps of obtaining graphene flakes or graphite oxide S10, forming amixture with additives, polymers and pore-forming agents S20, pouringthe suspension into a mold, and applying a heat treatment 400° C. first,then to 2000° C. preferring 1800° C. in a reduction gas flow environmentS30. Graphene-based porous carbon nanocomposites sheet is prepared,which has high surface area, extremely high tensile and Young's modulus.Pore sizes are in the range of 1 nm to 8 μm.

As shown in FIG. 5 , the method of the present invention generallycomprises the steps of applying a porous graphene carbon plate or sheetin a mold S10, forming the plate or sheet stacks via over-layer themS20, forming the parts or articles by applying vacuum in the mold,injecting resin to cure at 20° C. to 400° C. preferring 250° C. S30, andapplying the parts or articles to the desired vehicles S40. In apreferred embodiment and curing of the present invention the heatingprocess heats the fibers up to 400° C., preferring 250° C. in air S30.

FIG. 6 provides the graphene composite compound pellets and thecorresponding graphene-based carbon fibers that can be used to form someintelligent machine parts as it did using PAN conventional carbonfibers. The processing of those fibers have low cost manufacturingcompared to PAN carbon fibers. Only intelligent articles from thisinvention will be selected with its mechanical strength matchingaluminum/magnesium (Al—Mg) alloys and some of the parts as the same assteels.

FIG. 7 shows the graphene gel that is formed by mixing graphene powderwith epoxy. Then at low heating conditions, it is cured by heating andform a machine article with 3D molding. Similar designed articles andprocessing can be used for intelligent machine or vehicle parts, orliquid transportation pipes such as working in chemical plants and inthe ocean to avoid corrosion. Graphene-based composites are excellentfor having anti-corrosion properties while maintaining an excellentmechanical properties.

FIG. 8 shows a 3D printed trolley or wagon models. The 3D printingmaterials is a graphene-based ABS composite filament. This model hasbody size of 10 cm×4 cm×2 cm, and thickness of printing is 1 mm, butonly weighs 0.5 gram. The same volume size of steel have weight about 30grams, decreasing 80% of the conventional steel wagon weight.

FIG. 9 shows embodiments of components that are produced from thisinvention through the foaming agent added into graphene gel. Thosegraphene foams can be cut into a satisfactory shape, and, using epoxy,to make the machine articles formed after cured either by UV light or byheating.

What is claimed is:
 1. A method of producing graphene-based carbon fibercomprising the steps of: creating a mixture; heating the mixture to atemperature of between 20° to 400° C.; forming a plurality of porouscarbon fiber sheets, a pore size of the pores being in a range of 1 nmto 8 μm; and annealing the plurality of porous carbon fiber sheets at atemperature of 400° C. to 2000° C. after the heating step.
 2. The methodof claim 1 further comprising the step of dispersing a quantity of atleast one of a graphene powder, graphene flakes, graphene oxide powder,or graphene oxide flakes into a solvent solution with a surfactant toform the mixture.
 3. The method of claim 2 wherein the solvent solutionis one of water, an alcohol, acetone, ketone, dimethyl formamide (DMF),ethylene glycol (EG), or DMSO.
 4. The method of claim 1 furthercomprising the step of adding at least one of a nanocellulose fiber, apolymer, and a resin into a solvent solution with a surfactant to formthe mixture.
 5. The method of claim 4 wherein the adding step comprisesadding the polymer to the solvent solution with the surfactant, whereinthe polymer is one of polyacrylonitrile (PAN), polystyrene, portion ofasphalt, epoxy, polycarbonate, and any kind of cellulose, polyvinylalcohol (PVA), polyurethane, polyvinyl chloride (PVC), polyethylene(PE), polyethylene glycol, nylon, polydimethylsiloxane, polyacrylamide,and poly(methyl methacrylate) (PMMA).
 6. The method of claim 4 whereinthe adding step comprises adding the resin to the solvent solution withthe surfactant, wherein the resin is one of a polyvinyl resin, polyesterresin, epoxy, polycarbonate resin, polyurethane resin, silicone resin,poly(methyl methacrylate) resin, and an epoxy siloxane resin.
 7. Themethod of claim 1 wherein the mixture comprises a quantity of at leastone of a graphene powder, graphene flakes, graphene oxide power, orgraphene oxide flakes in a solvent solution with a surfactant, and atleast one of a nanocellulose fiber, a polymer, and a resin.
 8. Themethod of claim 1 further comprising the steps of: dispersing a quantityof at least one of a graphene powder, graphene flakes, graphene oxidepowder, and graphene oxide flakes into a solvent solution with asurfactant, and adding at least one of a nanocellulose fiber, a polymer,and a resin into the solvent solution with the surfactant to form themixture.
 9. The method of claim 8 wherein the mixture comprises thequantity of at least one of the graphene powder, graphene flakes,graphene oxide powder, and graphene oxide flakes in the solvent solutionwith the surfactant and the at least one of the nanocellulose fiber, thepolymer, and the resin.
 10. The method of claim 8 further comprising astep of adding an additive to the solvent solution with the surfactant,the additive being at least one of nanoparticles or nanowires of metal,steel nano-powder, carbon nanotubes, and a metal oxide, and combinationsthereof.
 11. The method of claim 1 further comprising the step ofstirring the mixture to obtain a uniform viscosity mixture.
 12. Themethod of claim 11 wherein the step of heating the mixture comprises thestep of heating the uniform viscosity mixture.
 13. The method of claim 1wherein the step of forming the plurality of carbon fiber sheets furthercomprises using a 3D printing machine.
 14. The method of claim 13wherein the 3D printing machine is computerized and configured toperform the step of forcing the mixture through a nozzle onto asubstrate.
 15. The method of claim 14 wherein the forcing of the mixturethrough the nozzle forms a graphene-based composite filament.
 16. Themethod of claim 1 wherein the step of forming the plurality of porouscarbon fiber sheets is carried out under a vacuum.
 17. The method ofclaim 16 further comprising the steps of placing the sheets in a mold,injecting a quantity of second resin into the mold, and drawing thevacuum on the sheets and the second resin.
 18. The method of claim 17further comprising the steps of curing the second resin at approximately20° C.-400° C. forming a cured composition, the curing step formingchemical bonds to enhance mechanical strength.
 19. A method of forming acarbon fiber item using a plurality of carbon fiber sheets comprisingthe steps of: layering the plurality of carbon fiber sheets; applying aresin to the plurality of carbon fiber sheets; and curing the resin; andannealing the cured resin and the plurality of carbon fiber sheets in aninert gas at a temperature of 1,800° C.
 20. The method of claim 19further comprising the step of cutting the carbon fiber item to adesired shape.